While reacting the sterically demanding triphosphaferrocene [Cp*Fe(η(5)-P3C2Mes2)] () with Cu(i) halides, the sandwich complex undergoes an unprecedented fragmentation into decamethylferrocene, FeX2 (X = Cl, Br, I) and [P3C2Mes2](-) units. Subsequently, these phospholyl ligands act as versatile, negatively charged building blocks for the formation of supramolecular aggregates representing the monomeric, dimeric and polymeric (1D and 2D) coordination compounds [(P3C2Mes2)2{Cu7(CH3CN)7(μ4-X)(μ3-X)2(μ-X)}{Cu2(μ2-X)2X}{Cu(CH3CN)(μ2-X)}]2·6CH3CN (·6CH3CN: X = Cl, ·6CH3CN: X = Br), [(P3C2Mes2)2{Cu(CH3CN)}6(μ-Br)2(μ3-Br)2{Cu(CH3CN)2Br}2]·CH3CN (·CH3CN), [(P3C2Mes2)4{Cu5(CH3CN)5(μ2-Br)}{Cu(CH3CN)2CuBr2}2{Cu(CH3CN)2}]n(+)[CuBr2]n(-)·2CH3CN (·2CH3CN), [(P3C2Mes2){Cu(CH3CN)(μ-I)}4{Cu(CH3CN)3}]·0.5C7H8·2.5CH3CN (·0.5C7H8·2.5CH3CN), [(P3C2Mes2)Cu7(CH3CN)4(μ4-I)2(μ3-I)2(μ-I)2]x·2C7H8 (·2C7H8), [(P3C2Mes2){Cu(CH3CN)3}2{Cu(μ-I)}6]·0.5CH2Cl2·3CH3CN (·0.5CH2Cl2·3CH3CN) and [Cp*Fe(CH3CN)3]n(+)[(P3C2Mes2)2{Cu(CH3CN)2}{Cu(μ-I)}6]n(-)·0.6CH2Cl2 (·0.6CH2Cl2) with rather non-typical structural motifs within the large varieties of copper halide chemistry. Besides the X-ray structural analyses the obtained assemblies were also characterized in solution in which they undergo fragmentation and re-aggregation processes.